The present invention relates to a silver halide photographic material, a photographic material containing thin tabular grains, and a method for producing the same.
Silver halide grains are generally produced by the reaction of a silver salt aqueous solution and a halide salt aqueous solution in a colloidal aqueous solution in a reaction solution. That is, a single jet method of pouring a protective colloid represented by gelatin and a halide salt aqueous solution into a reaction vessel and adding a silver salt aqueous solution thereto with stirring the above aqueous solution, and a double jet method of pouring a gelatin aqueous solution into a reaction vessel, and adding a halide salt aqueous solution and a silver salt aqueous solution thereto are known. Comparing both methods, silver halide grains having narrow grain size distribution can be obtained by a double jet method, and the halide composition can be changed freely with the growth of the grains.
Further, it is known that the growing speed of silver halide-grains is largely influenced by the concentration of silver ions (halide ions) in a reaction vessel, the concentration of a silver halide solvent, the distance between grains and the grain size. In particular, the uniformity in concentration of silver ions or halide ions produced of a silver salt aqueous solution and a halide salt aqueous solution added to a reaction vessel differs in growing speed by each concentration, which results in the formation of a heterogeneous silver halide emulsion. For preventing this ununiformity, it is necessary to make the reaction of a silver salt aqueous solution and a halide salt aqueous solution supplied into a colloidal aqueous solution by rapid and uniform mixture so as to make the concentration of silver ions or halide ions in a reaction vessel uniform. However, it has been difficult to produce homogeneous silver halide grains by prior art techniques of the addition of a halide salt aqueous solution or a silver salt aqueous solution, since an area where the concentration of halide ions or silver ions is high is brought about in the vicinity of the place of addition of each reaction solution.
For resolving the uniform distributions of concentrations of silver ions and halide ions as above, a trial for growing silver halide grains has been made by providing a reaction vessel with a mixer separately, and supplying a silver salt aqueous solution and a halide salt aqueous solution to the mixer, and mixing the aqueous solutions rapidly. For example, there are disclosed in JP-A-53-37414 (the term xe2x80x9cJP-Axe2x80x9d as used herein means an xe2x80x9cunexamined published Japanese patent applicationxe2x80x9d) and JP-B-48-21045 (the term xe2x80x9cJP-Bxe2x80x9d as used herein means an xe2x80x9cexamined Japanese patent publicationxe2x80x9d) a method of circulating a protective colloid aqueous solution (containing silver halide grains) in a reaction vessel from the bottom of the reaction vessel by a pump, providing the reaction vessel with a mixer midway in the circulating system, supplying a silver salt aqueous solution and a halide salt aqueous solution to the mixer, and mixing the aqueous solutions rapidly in the mixer, to thereby grow silver halide grains, and an apparatus used for that purpose. A method of circulating a protective colloid aqueous solution (containing silver halide grains) in a reaction vessel from the bottom of the reaction vessel by a pump, and pouring a halide salt aqueous solution and a silver salt aqueous solution by a pump midway in the circulating system is disclosed in U.S. Pat. No. 3,897,935. A method of circulating a protective colloid aqueous solution in a reaction vessel (containing silver halide grains) by a pump from the reaction vessel, pouring a halogenated alkali metal salt aqueous solution, diffusing the aqueous solution until it becomes homogeneous, and thereafter pouring a silver salt aqueous solution to the system and mixing them, to thereby form silver halide grains, and an apparatus used for that purpose are disclosed in JP-A-53-47397. It is certainly possible to independently change the flow of an aqueous solution in a reaction vessel and the stirring efficiency of a mixer in a circulating system according to these methods, therefore, grains can be grown on more uniform condition of concentration distribution. However, silver halide crystal fed from a reaction vessel with a protective colloid aqueous solution is eventually subjected to uniform and rapid growth at the inlets of a halide salt aqueous solution and a silver salt aqueous solution. Therefore, it is theoretically impossible to get rid of the concentration distribution in the vicinity of a mixing zone or the inlets of aqueous solutions, thus the object of growing silver halide grains uniformly cannot be achieved.
As one means for solving this problem fundamentally, a method of growing silver halide grains in a reaction vessel by adding fine grains which have been formed in advance in an external mixer to the reaction vessel is disclosed in U.S. Pat. Nos. 5,035,991, 5,270,159, 5,250,403, EP 274852, EP 523842 and Japanese Patent 2684397. According to this method,a silver and a halogen seed are fed as silver halide fine grains. Since the silver halide fine grains are spread all over the reaction vessel, and then dissolved and silver ions and halide ions are supplied at the same time, the distributions of concentrations of silver ions and halide ions are largely improved (become uniform).
However, when fine grains supplied from an external mixer are large in size, time is taken to dissolve the fine grains, which causes inefficiency such that grain formation is prolonged. It is disclosed in Japanese Patent Nos. 2,008,051 and 2,060,301 that low temperature formation is effective to form small size silver halide grains. However, gelatin which is the most ordinary dispersion medium coagulates at low temperature, and it is very difficult to form grains at 30xc2x0 C. or lower. In particular, continuous nucleation is difficult in a closed type external mixer due to the generation of clogging. For the solution of this problem, JP-B-7-111550 discloses that silver halide grains can be formed even at temperature as low as 15xc2x0 C. or lower without being accompanied by coagulation of a reaction solution by using gelatin or synthetic protective colloid having a lowered molecular weight.
As described above, in the techniques of growing silver halide grains by feeding fine grains, the miniaturization of the fine grains for supply has been contrived, but the size distribution of the fine grains to be supplied is far from satisfaction, and the size of the fine grains disclosed in JP-B-7-111550 is 20 nm or greater. Therefore, finer grains have been earnestly desired.
On the other hand, tabular silver halide grains are ordinarily used in photographic materials, in particular, photographic materials for photographing. The reason is mainly because tabular silver halide grains have a great surface area/volume ratio and this is advantageous to spectral sensitization. That is, silver halide having light absorption sensitivity only in a blue region is generally spectrally sensitized by adsorbing a sensitizing dye onto the surface of a grain, and tabular grains having a great surface area/volume ratio have a large dye adsorption amount per a grain, thus light absorption amount increases and high sensitivity can be achieved. Therefore, studies of making a surface area/volume ratio greater have been advanced. In particular, as an effective means to form a thin tabular grain, a method of restricting the growth of a tabular grain in the thickness direction by making use of a crystal phase-controlling agent is known. The examples of these methods are disclosed in U.S. Pat. Nos. 5,411,853, 5,418,125 and JP-A-10-104769, but a crystal phase-controlling agent is not preferred, since it is competitive with the adsorption of a sensitizing dye. The techniques of forming a thin tabular grain without using a crystal phase-controlling agent is disclosed in U.S. Pat. No. 4,713,320 and JP-A-11-108536, but these methods are not sufficient and the technique capable of forming a thinner tabular grain is required.
Further, it has been found from the results of our study that when tabular grains are grown by adding fine grains, dissolving and depositing them on tabular grains, non-twin crystal fine grains are preferred as the fine grains. The reason is that if twin crystal grains are contained in the fine grains, the twin crystal grains are easy to grow, which causes inefficiency such that the resulting grains become polydispersed grains. Methods of adding non-twin crystal fine grains to a seed crystal emulsion and growing the seed crystal emulsion are disclosed in JP-A-4-34544, JP-A-4-330427 and JP-A-11-202435, but these patent do not disclose that the fine grains are formed on high pH condition.
The objects of the present invention are to provide a silver halide photographic material of high sensitivity, in particular, to accomplish the above object using thin tabular grains by an improved fine grain addition-growing method, and to provide fine grains for growth which makes it possible to form the tabular grains.
These and other objects of the present invention have been achieved by the following means:
(1) A producing method of a silver halide emulsion comprising the steps of adding silver halide fine grains AgX0 (X0 means chloride, bromide, iodide or a mixture of their 2 or 3 components, preferably AgX0 has an AgBr content of from 60to 100 mol %) to a silver halide seed crystal emulsion containing at least water, dispersion medium 1 and silver halide crystal, and growing the seed-crystal by dissolving the added AgX0, wherein AgX0 are formed indispersion medium solution 2 containing dispersion medium 2, the pH of dispersion medium solution 2 of the time when AgX0 are formed is from 7.3 to 12.2, the average equivalent-circle (projected area) diameter of AgX0 is from 0.001 to 0.2 xcexcm, and AgX0 are non-twin crystal grains not substantially having twin planes.
(2) The producing method of a silver halide emulsion as described in the above item (1), wherein the temperature of dispersion medium 2 of the time when AgX0 are formed is from 0 to 10xc2x0 C.
(3) The producing method of a silver halide emulsion as described in the above item (1), wherein the variation coefficient of the equivalent-circle diameter of AgX0 is 20% or less.
(4) The producing method of a silver halide emulsion as described in the above item (1), wherein the average equivalent-circle diameter,of AgX0 is 20 nm or less.
(5) The producing method of a silver halide emulsion as described in the above item (1), wherein AgX0 are fine grains formed by a batch system of adding a silver salt solution and a halide salt solution to dispersion medium solution 2 in a reaction vessel by a double jet method.
(6) The producing method of a silver halide emulsion as described in the above item (1), wherein AgX0 are fine grains formed by a continuous system of continuously supplying a silver (Ag+) salt solution and a halide (Xxe2x88x92) salt solution to a continuous mixer through a hollow pipe, mixing both solutions in the mixer, and continuously discharging the mixed solution through a feed pipe.
(7) The producing method of a silver halide emulsion as described in the above item (5) or (6), wherein at least one of a silver (Ag+) salt solution and a halide (Xxe2x88x92) salt solution to be added contains from 0.01 to 15 mass % of dispersion medium 3.
(8) A silver halide photographic material having at least one light-sensitive emulsion layer containing the silver halide grains produced by the producing method of a silver halide emulsion as described in the above item (1), wherein grains having an aspect ratio of 10 or more occupy 50% or more of the total projected area of all the silver halide grain and the silver halide grain have an average thickness of 0.05 xcexcm or less.
(1) A producing method of a silver halide emulsion comprising the steps of adding silver halide fine grains AgX0 preferably having an AgBr content of from 60 to 100 mol % (AgBr0), more preferably from 80 to 100 mol %, and further more preferably from 90 to 100 mol %, to a silver halide seed crystal emulsion containing at least water, dispersion medium 1 and silver halide seed crystal, and growing the seed crystal by dissolving and depositing the added AgX0 on the seed crystal, wherein AgX0 are formed in dispersion medium solution 2 containing dispersion medium 2 by reacting silver ion (Ag+) and halide ion (Xxe2x88x92), the pH of dispersion medium solution 2 of the time when AgX0 are formed is from 7.3 to 12.2, preferably from 8.0 to 1.2.0, and more preferably from 9.5 to 11.7, the average equivalent-circle (projected area) diameter of AgX0 is from 0.001 to 0.2 xcexcm, preferably from 0.002 to 0.1 xcexcm, more preferably from 0.002 to 0.05 xcexcm, and still more preferably from 0.002 to 0.02 xcexcm, and AgX0 are non-twin crystal fine grains not substantially having twin planes.
(2) The producing method of a silver halide emulsion as described in the above item (1), wherein AgX0 are fine grains formed by a batch system of adding an Ag+ salt solution and an Xxe2x88x92 salt solution to dispersion medium solution 2 in a reaction vessel by a double jet method.
(3) The producing method of a silver halide emulsion as described in the above item (1), wherein AgX0 are fine grains formed by a continuous system of continuously supplying the Ag+ salt solution and the Xxe2x88x92 salt solution to a continuous mixer through a hollow pipe, mixing both solutions in the mixer, and continuously discharging the mixed solution through a feed pipe.
(4) The producing method of a silver halide emulsion as described in the above item (1), wherein the temperature of dispersion medium solution 2 of the time when AgX0 are formed is from 0 to 40xc2x0 C., preferably from 0 to 20xc2x0 C., more preferably from 0 to 15xc2x0 C., and still more preferably from 0 to 10xc2x0 C.
(5) The producing method of a silver halide emulsion as described in the above item (2) or (3), wherein at least one of the Ag+ salt solution and the Xxe2x88x92 salt solution to be added, preferably both of them, contains from 0.01 to 15 mass % (i.e., weight %), preferably from 0.05 to 5 mass %, of dispersion medium 3.
(6) The producing method of a silver halide emulsion as described in the above item (2) or (3), wherein the pH of an Xxe2x88x92 salt solution to be added when AgX0 are formed is from 7.3 to 12.2, preferably from 8.0 to 12, and more preferably from 9.3 to 12.
(7) The producing method of a silver halide emulsion as described in the above item (2) or (3), wherein the temperature of at least one of the Ag+ salt solution and the Xxe2x88x92 salt solution to be added, preferably both of them, is from 0 to 40xc2x0 C., preferably from 0 to 25xc2x0 C., and more preferably from 0 to 10xc2x0 C.
(8) The producing method of a silver halide emulsion as described in the above item (1), wherein the pH of dispersion medium solution 2 during at least a period of nucleation at AgX0 formation falls within the pH range as described in the above item (1).
(9) The producing method of a silver halide emulsion as described in the above item (8), wherein the period of nucleation of AgX0 is the period of time of 5 seconds from the start of simultaneous mixed addition of Ag+ and Xxe2x88x92 to dispersion medium solution 2, preferably 30 seconds, more preferably 2 minutes, and still more preferably 6 minutes.
(10) The producing method of a silver halide emulsion as described in the above item (8), wherein dispersion medium solution 2 during the period of nucleation of AgX0 is a dispersion medium solution present in the area in the hollow pipe through which the added Ag+ and Xxe2x88x92 travel during the period of time of 5 seconds from the start of addition, preferably 30 seconds, more preferably 2 minutes, and still more preferably 6 minutes.
(11) The producing method of a silver halide emulsion as described in any of the above items. (8) to (10), wherein an acid is added to the emulsion containing AgX0 during the time after the period of nucleation of AgX0 until the addition of the AgX0 emulsion to the seed crystal emulsion, and the AgX0 emulsion is added to the seed crystal emulsion after the pH of the AgX0 emulsion has been lowered by 0.3 to 10, preferably by 0.6 to 10, and more preferably by 1.0 to 10.
(12) The producing method of a silver halide emulsion as described in the above item (1) or (8), wherein the variation width of pH during the period of nucleation of AgX0 or during the period of formation of the AgX0 emulsion is within xc2x11.0, and preferably within xc2x10.2.
(13) The producing method of a silver halide emulsion as described in the above item (1) or (5), wherein the concentration of dispersion medium 1 or 2 or 3 is from 0.1 to 20 mass %, and preferably from 0.1 to 10 mass %.
(14) The producing method of a silver halide emulsion as described in the above item (1) or (5), wherein dispersion medium 1 or 2 or 3 is gelatin, and the methionine (Met) group content in the gelatin is from 0 to 25 xcexcmol/g, preferably from 0 to 5 xcexcmol/g, and more preferably from 0 to 1 xcexcmol/g.
(15) The producing method of a silver halide emulsion as described in the above item (1), wherein the content of Met group in gelatin in the AgX0 emulsion is reduced to 0 to 90% of the content before the start of the addition, preferably from 0 to 30%, and more preferably from 0 to 10%, during the time after the period of nucleation of AgX0 until the addition of the AgX0 emulsion to the seed crystal emulsion.
(16) The producing method of a silver halide emulsion as described in the above item (1), (4) or (13) , wherein the viscosity (10xe2x88x923Paxc2x7s) of dispersion medium solution 2 is from 1.0 to 80, preferably from 1.0 to 40, and more preferably from 1.0 to 10, when allowed to stand for 30 minutes on temperature condition as described in the above item (4).
(17) The producing method of a silver halide emulsion as described in the above item (4), wherein the AgX0 emulsion is formed after the temperature of dispersion medium solution 2 has been lowered by 1 to 30xc2x0 K, and preferably by 5 to 30xc2x0 K, by adding a coolant of from 1 to 290xc2x0 K, and preferably from 50 to 280xc2x0 K to dispersion medium solution 2.
(18) The producing method of a silver halide emulsion as described in the above item (17), wherein the coolant is an ice having an H2O content of from 70 to 100%, preferably from 97 to 100%, liquefied gas or dry ice.
(19) The producing method of a silver halide emulsion as described in the above item (1), (13) or (14), wherein dispersion medium 1 or 2 or 3 contains low molecular weight gelatin having a molecular weight of from 3,000 to 5xc3x97104, preferably from 5,000 to 2xc3x97104, in an amount of from 25 to 100 mass %, preferably from 70 to 100 mass %, and more preferably from 95 to 100 mass %.
(20) The producing method of a silver halide emulsion as described in the above item (19), wherein the low molecular weight gelatin is low molecular weight gelatin produced by adding an acid to a gelatin aqueous solution, and then hydrolyzing the gelatin or collagen in the aqueous solution on an acidic condition of pH of from xe2x88x921 to 5, preferably from xe2x88x920.5 to 3, to thereby lower the molecular weight.
(21) The producing method of a silver halide emulsion as described in the above item (19), wherein the low molecular weight gelatin is low molecular weight gelatin produced by adding an alkali agent to a gelatin aqueous solution, and then hydrolyzing the gelatin or collagen in the aqueous solution on an alkaline condition of pH of from 8 to 15, preferably from 10 to 14, to thereby lower the molecular weight.
(22) The producing method of a silver halide emulsion as described in the above item (20), wherein the acid is one or more oxo acid(s).
(23) The producing method of a silver halide emulsion as described in the above item (20) or (21), wherein the gelatin is gelatin produced by removing from 5 to 100%, preferably from 50 to 100%, and more preferably from 90 to 100%, of the acid or base added from the gelatin aqueous solution by one or more methods described below after the molecular weight of the gelatin has been lowered,
a1) a method of subjecting the gelatin solution to ultra-filtration,
a2) a method of subjecting the gelatin solution to electrodialysis,
a3) a method of subjecting the gelatin solution to washing with water after being subjected to gelation,
a4) a method of adding a flocculation-precipitant to the gelatin solution to flocculate and precipitate the gelatin, and then separating and collecting the flocculated product,
a5) a method of adding a water-soluble organic solvent (e.g., methanol or ethanol) to the gelatin solution to flocculate and precipitate the gelatin, and then separating and collecting the flocculated product,
a6) a method of bringing the gelatin solution into contact with washing water via a semipermeable membrane, wherein the semipermeable membrane is a membrane which is permeable to a water molecule, ions and molecules having a molecular weight of 500 or less but is impermeable to molecules having a molecular weight of 3,000 or more,
a7) a method of bringing the gelatin solution into contact with an ion exchange resin.
(24) The producing method of a silver halide emulsion as described in any of the above items (19) to (21), wherein the low molecular weight gelatin is used, after the molecular weight of the gelatin has been lowered, by adding a base or an acid to the gelatin solution to adjust the pH of the solution to 2 to 12.5, preferably 2 to 11, more preferably from 3 to 10.
(25) The producing method of a silver halide emulsion as described in any of the above items (20) to (22), wherein the low molecular weight gelatin is used after the molecular weight of the gelatin has been lowered, with 1 to 100%, preferably from 10 to 100%, and more preferably from 30 to 100%, of the base or acid added being remaining in the gelatin.
(26) The producing method of a silver halide emulsion as described in any of the above items (1) to (13) , wherein dispersion medium 1 or 2 or 3 is gelatin, and from30 to 100 mass %, preferably from 60 to 100 mass %, and more preferably from 90 to 100 mass %, of the gelatin has a hydroxyproline (Hyp) content (the number of Hyp groups per 1,000 amino acid residues) of from 0 to 100, preferably from 0 to 80, more preferably from 0 to 40, and still more preferably from 0 to 10.
(27) The producing method of a silver halide emulsion as described in the above item (26), wherein the gelatin is gelatin extracted from the animal living in the frigid zone or the frigid sea of the temperature of from xe2x88x9250 to 25xc2x0 C., preferably from xe2x88x9250 to 15xc2x0 C., and more preferably from xe2x88x9250 to 5xc2x0 C., preferably extracted from the bone, skin or scale of the animal living in the frigid sea, and more preferably extracted from the skin of the fish living in the frigid sea.
(28) The producing method of a silver halide emulsion as described in the above item (26) or (27), wherein the methionine (Met) group content of the gelatin is reduced to 0 to 90% of the Met content of the collagen protein in the original animal, preferably from 0 to 40%, and more preferably from 0 to 10%.
(29) The producing method of a silver halide emulsion as described in the above item (26) or (27), wherein the histidine (His) group content of the gelatin is reduced to 0 to 90% of the His group content of the original natural collagen, preferably from 0 to 40%, and more preferably from 0 to 10%.
(30) The producing method of a silver halide emulsion as described in any of the above items (1) to (13), wherein dispersion medium 1 or 2 or 3 is gelatin, and from 10 to 100%, preferably from 30 to 100%, and more preferably from 60 to 100%, of the carboxyl groups in from 30 to 100 mass % of the gelatin, preferably from 60 to 100 mass %, and more preferably from 90 to 100 mass %, are chemically modified.
(31) The producing method of a silver halide emulsion as described in the above item (1), (5) or (13), wherein from 1 to 100 mass %, preferably from 10 to 90 mass %, and more preferably from 20 to 70 mass %, of dispersion medium 1 or 2 or 3 comprises a water-soluble synthetic high polymer having a molecular weight of from 103 to 106, and preferably from 103 to 105 produced by polymerizing from one to twenty kinds, and preferably from one to ten kinds, of monomers.
(32) The producing method of a silver halide emulsion as described in the above item (13) or (31), wherein the synthetic high polymer is not subject to gelation (the state where the viscosity (10xe2x88x923Paxc2x7s) is 100 or more, preferably 50 or more) when a 3 mass % aqueous solution of the water-soluble synthetic high polymer, preferably a 5 mass % aqueous solution (pH of from 2 to 12), is allowed to stand at 1 to 15xc2x0 C., preferably from 1 to 8xc2x0 C., for 30 minutes.
(33) The producing method of a silver halide emulsion as described in the above item (1), wherein the total concentration of the inorganic ions in dispersion medium solution 2 at the time of the start of formation of the fine grains is from 0 to 1 mol/liter, preferably from 0 to 0.2 mol/liter, and more preferably from 0 to 0.02 mol/liter.
(34) The producing method of a silver halide emulsion as described in the above item (1), wherein the concentration of the excess amount of Ag+ or Xxe2x88x92 in dispersion medium solution 2 at the start of AgX0 formation is preferably from 0 to 10xe2x88x921.6 mol/liter, more preferably from 0 to 10xe2x88x922 mol/liter, and still more preferably from 0 to 102.3 mol/liter.
(35) The producing method of a silver halide emulsion as described in the above item (1), wherein the twin plane formation inhibitor described in the following a10) is added to dispersion medium solution 2 at AgX0 formation, preferably at the start of AgX0 formation, in an amount of from 10xe2x88x928 to 1 mol/liter, preferably from 10xe2x88x927 to 0.1 mol/liter, to thereby reduce the ratio of the number of grains having two or more twin planes in one grain, or the ratio of the number of grains having one or more twin planes in one grain, to 0 to 90%, preferably from 0 to 40%, and more preferably from 0 to 10%, of the number of grains at the time not containing the twin plane formation-inhibitor:
Compounds a10):
(i) compounds containing one or more onium salt groups in one molecule and excluding gelatin and NH4+, preferably compounds also excluding ammonium compounds having two or less carbon atoms, and more preferably compounds having from one to three pyridinium salt groups in one molecule,
(ii) aromatic compounds having one or more iodo groups and one or more xe2x80x94OH groups substituted on an aromatic ring,
(iii) nitrogen-containing heterocyclic compounds, which contains, in one molecule, one or more heterocyclic rings having two or more nitrogen atoms in a 4- to 7-membered ring,
(iv) cyanine dyes,
(v) compounds having a divalent sulfur group-containing heterocyclic group,
(vi) thiourea compounds,
(vii) amino thioethers, and
(viii) divalent sulfur group-containing organic compounds having 25 or less total carbon atoms.
(36) The producing method of a silver halide emulsion as described in the above item (2) or (3), wherein at least either one of the Ag+ salt solution and the Xxe2x88x92 salt solution, preferably both of them, is added from porous addition pores of from 2 to 1015, preferably from 8 to 1015, and more preferably from 30 to 1015.
(37) The producing method of a silver halide emulsion as described in the above item (36), wherein the porous addition pores or porous addition system having porous addition pores are composed of a rubber-like elastic body, and the rubber-like elastic body is a material which reversibly elastically deforms to the length of 1.05 to 20 times the original length in the working temperature region, preferably from 1.1 to 20 times, and more preferably from 1.3 to 10 times, and the rubber elastic modulus (=Young""s modulus (N/m2)) of the material is from 104 to 109, and preferably from 105 to 108.
(38) The producing method of a silver halide emulsion as described in the above item (36) or (37), wherein the addition pores are closed when addition is ceased, and an addition solution and a reaction solution are out of contact with each other.
(39) The producing method of a silver halide emulsion as described in the above item (1), wherein after the AgX0 emulsion has been formed, the AgX0 emulsion is subjected to ultrafiltration, and then the AgX0 emulsion is added to the seed crystal emulsion after the NO3xe2x88x92 content (mol/mol AgX) in the AgX0 emulsion has been reduced to 0 to 90% of the NO3xe2x88x92 content by being subjected to ultrafiltration, preferably from 0 to 40%, and more preferably from 0 to 10%.
(40) The producing method of a silver halide emulsion as described in the above item (23), (38) or (39), wherein the ultrafiltration is performed by cross flow system of feeding a solution in the parallel direction to a filtration film.
(41) The producing method of a silver halide emulsion as described in the above item (23), (38) or (39), wherein the. ultrafiltration is performed by using a hollow pipe type filtration film of feeding a solution into the hollow pipe.
(42) The producing method of a silver halide emulsion as described in the above item (1), wherein the AgX0 are fine grains not substantially having screw dislocation lines.
(43) The producing method of a silver halide emulsion as described in the above item (1), wherein silver halide fine grains AgI0 having an AgI content of from 80 to 100 mol %, preferably from 95 to 100 mol %, are added to the seed crystal emulsion in the growing method, and from 20 to 100% of the total content of Ixe2x88x92 added during growing, preferably from 60 to 100%, and more preferably from 90 to 100%, is added in the form of AgI0.
(44) The producing method of a silver halide emulsion as described in the above item (43), wherein the AgI0 are non-twin crystal fine grains not substantially having twin planes.
(45) The producing method of a silver halide emulsion as described in the above item (43), wherein the AgI0 are formed in fresh dispersion medium solution 2 and the pH of dispersion medium solution 2 of the time when AgI0 are formed is from 4 to 12, and preferably from 5 to 12.
(46) The producing method of a silver halide emulsion as described in the above item (1), wherein silver halide fine grains AgCl0 having an AgCl content of from 60 to 100 mol %, preferably from 80 to 100 mol %, are added to the seed crystal emulsion in the growing method, and from 20 to 100% of the total content of Clxe2x88x92 added during growing, preferably from 60 to 100%, and more preferably from 90 to 100%, is added in the form of AgCl0.
(47) The producing method of a silver halide emulsion as described in the above item (46), wherein the AgCl0 are non-twin crystal fine grains not substantially having twin planes.
(48) The producing method of a silver halide emulsion as described in the above item (46), wherein the AgCl0 are formed in fresh dispersion medium solution 2 by reacting Ag+ and Xxe2x88x92, and the pH of dispersion medium solution 2 of the time when AgCl0 are formed is from 1 to 12, preferably from 1 to 9, and more preferably from 1 to 6.
(49) The producing method of a silver halide emulsion as described in the above item (1), wherein the AgX0 are grains having multiple structure comprising a core layer and one or more shell layers, and the AgX composition between contiguous layers is different by 0.01 to 30 mol % in a AgCl content or an AgI content, preferablyby 0.01 to 10mol %, and more preferably by 0.1 to 15 mol %.
(50) The producing method of a silver halide emulsion as described in the above item (49), wherein the AgI content in the outermost shell layer is higher than the AgI content in the core layer in the multiple structure by 0.1 to 40 mol %, preferably by 1 to 30 mol %.
(51) The producing method of a silver halide emulsion as described in the above item (1), wherein the AgX0 contain, in the grains and/or on the surfaces of the grains, one or more simple atoms of atomic numbers of from 1 to 92 or compounds of the atoms as dopants, in a total amount of from 10xe2x88x929 to 10xe2x88x921 mol/mol AgX, and preferably from 10xe2x88x928 to 10xe2x88x922 mol/mol AgX.
(52) The producing method of a silver halide emulsion as described in the above item (51), wherein the dopant is a simple atom of a metal atom (atoms on the left side of the line connecting boron B and At in the Periodic Table (long period)), the neutral body or ion of the compound of the metal atom, more preferably a simple atom of a transition metal atom, the neutral body. or ion of the compound of a transition metal atom.
(53) The producing method of a silver halide emulsion as described in the above item (52), wherein the compound is a metal complex having from 1 to 3 metal atoms and from 2 to 20 ligands, and from 1 to all of the ligands are inorganic ligands and/or organic ligands having from 1 to 30 carbon atoms.
(54) The producing method of a silver halide emulsion as described in the above item (53), wherein the metal complex is a tetra- or hexa-coordinated complex.
(55) The producing method of a silver halide emulsion as described in the above item (51), wherein the dopant is a compound containing from 1 to 105 chalcogen atoms in one molecule.
(56) The producing method of a silver halide emulsion as described in the above item (55), wherein the dopant is a compound containing from 1 to 105 thiosulfonyl groups in one molecule.
(57) The producing method of a silver halide emulsion as described in the above item (55), wherein the dopant is a compound containing from 1 to 105 thiosulfonate groups in one molecule.
(58) The producing method of a silver halide emulsion as described in the above item (1), wherein the pH of the AgX0 emulsion immediately before being added to the seed crystal emulsion is from 2 to 11, preferably from 3 to 9, and more preferably from 4 to 8.
(59) The producing method of a silver halide emulsion as described in the above item (1), wherein the fine grains are formed, and the fine grains are added to the seed crystal emulsion when (the average diameter of the grains/the average diameter of the grains just after formation) (A14) reaches 1 to 3, preferably from 1 to 2, and more preferably from 1 to 1.3.
(60) The producing method of a silver halide emulsion as described in the above item (1), wherein the reaction vessel for forming the fine grains is installed in the range of preferably from 0 to 100 m from the reaction vessel for growing the seed crystal, and more preferably from 0 to 10 m.
(61) The producing method of a silver halide emulsion as described in the above item (1), wherein after the AgX0 emulsion has been formed, the AgX0 emulsion (which means emulsion containing at least one of AgBr0, AgI0, AgCl0 and AgX0) is subjected to ultrafiltration, and the AgX0 emulsion is added to the seed crystal emulsion after the volume of the AgX0 emulsion has been reduced to 1 to 90% of the volume before being subjected to ultrafiltration, preferably from 1 to 60%, and more preferably from 1 to 30%.
(62) The producing method of a silver halide emulsion as described in the above item (14), (15) or (28), wherein the reduction of the Met group content is performed by adding an oxidant, preferably H2O2, to the gelatin aqueous solution, to thereby oxidize Met groups.
(63) The producing method of a silver halide emulsion as described in the above item (1), wherein an antifoggant and/or a cyanine dye is added to dispersion medium solution 2 when AgX0 are formed in an amount of from 10xe2x88x928 to 10xe2x88x921 mol/liter, and preferably from 10xe2x88x927 to 10xe2x88x922 mol/liter.
(64) The producing method of a silver halide emulsion as described in the above item (1), (13) or (14), wherein dispersion medium 1 or 2 or 3 is gelatin having ad-molecules by covalent bonding by 0.1 to 80 molecules per one molecule, preferably from 0.1 to 20 molecules on average, and when the molecules are added to the AgX0 emulsion at 40xc2x0 C. in the state of 40 to 50% of saturated adsorption amount, an adsorption equilibrium constant K (the number of molecules in the state of adsorption/the number of molecules in the state of non-adsorption) is from 3 to 108, preferably from 10 to 108, and more preferably from 100 to 108.
(65) The producing method of a silver halide emulsion as described in the above item (1), wherein dispersion medium 1 or 2 or 3 is gelatin, and the Met group content in the gelatin is from 25.1 to 60 xcexcmol/g.
(66) The producing method of a silver halide emulsion as described in the above item (1), wherein dispersion medium 1 or 2 or 3 has a weight average molecular weight of from 3,000 to 106.
(67) The producing method of a silver halide emulsion as described in the above item (1) or (66), wherein dispersion medium 1 or 2 or 3 has from 2 to 10 peaks in a molecular weight distribution curve.
(68) The producing method of a silver halide emulsion as described in the above item (1), (43) or (46), wherein after the AgBr0 or AgI0 or AgCl0 have been formed, a flocculation-precipitant is added to flocculate and precipitate the emulsion, a supernatant is removed, and then the AgBr0 or AgI0 or AgCl0 are added to the seed crystal emulsion.
(69) The producing method of a silver halide emulsion as described in the above item (68), wherein the flocculation-precipitant is an organic sulfonic acid having from 1 to 105 carbon atoms, preferably from 1 to 103 or a salt thereof, and the addition amount is from 1 to 25 mass % of the gelatin in the emulsion, preferably from 3 to 15 mass %.
(70) The producing method of a silver halide emulsion as described in the above item (1), wherein from 60 to 100%, preferably from 90 to 100%, and more preferably from 97 to 100%, of the total projected area of the seed crystal grains of the seed crystal emulsion is occupied by tabular grains having a thickness of from 0.01 to 0.4 xcexcm, preferably from 0.01 to 0.2 xcexcm, more preferably from 0.01 to 0.1, and still more preferably from 0.01 to 0.05, an aspect ratio [circle-equivalent (projected area) diameter (xcexcm)/thickness (xcexcm)] of from 1.2 to 200, preferably from 2 to 200, and more preferably from 5 to 200, and a grain diameter of from 0.1 to 5 xcexcm, and preferably from 0.1 to 2 xcexcm.
(71) The producing method of a silver halide emulsion as described in the above item (1), wherein from 60 to 100%, preferably from 90 to 100%, and more preferably from 97 to 100%, of the total projected area of the AgX grains of the AgX emulsion finally obtained by the growth of the seed crystal grains is occupied by tabular grains having a thickness of from 0.01 to 0.5 xcexcm, preferably from 0.01 to 0.2 xcexcm, more preferably from 0.01 to 0.1, and still more preferably from 0.01 to 0.05, an aspect ratio of from 2 to 500, preferably from 10 to 500, and more preferably from 30 to 500, and a grain diameter of from 0.2 to 20 xcexcm, and preferably from 0.5 to 10 xcexcm.
(72) The producing method of a silver halide emulsion as described in the above item (70) or (71), wherein the tabular grain is a {111} tabular grain having {111} planes as principal planes and two twin planes parallel to the principal planes in the grain.
(73) The producing method of a silver halide emulsion as described in the above item (70) or (71), wherein the tabular grain is a {100} tabular grain having {100} planes as principal planes.
(74) The producing method of a silver halide emulsion as described in the above item (73), wherein the tabular grain has from 1 to 5 screw dislocation lines in the grain, and preferably from 1 to 3.
(75) The producing method of a silver halide emulsion as described in the above item (70), wherein the tabular seed crystal grains are formed through the stages of at least from nucleation to ripening, and the number average projected area diameter of the nuclei at the point of the termination of nucleation (at the point when the addition of Ag+ for nucleation is terminated) is from 1 to 40 nm, preferably from 1 to 20 nm, and more preferably from 1 to 10 nm.
(76) The producing method of a silver halide emulsion as described in the above item (70), (71) or (72), wherein the distance between the outermost twin planes of the {111} tabular grain (the distance between the twin plane closest to one principal plane and the twin plane closest to another principal plane) is from 1 to 30 nm, preferably from 1 to 15 nm, and more preferably 0 to 10 nm.
(77) The producing method of a silver halide emulsion as described in the above item (1), wherein in the growing method of the seed crystal, the seed crystal emulsion is subjected to ultrafiltration during the growing of the seed crystal, and the increasing amount of the seed crystal emulsion by the addition of the fine grain emulsion is reduced to 3 to 90% of the increasing amount of the time not performing ultrafiltration, preferably from 3 to 60%, and more preferably from 5 to 40%.
(78) The producing method of a silver halide emulsion as described in the above item (1), wherein in the growing method of the seed crystal, the seed crystal emulsion is subjected to ultrafiltration during the growing of the seed crystal, and the total amount of the seed crystal emulsion at the termination of the growing of the seed crystal is reduced to 10 to 90% of the total amount of the time not performing ultrafiltration, preferably from 10 to 60%, and more preferably from 10 to 40%.
(79) The producing method of a silver halide emulsion as described in the above item (70) or (72), wherein the nucleation of the seed crystal is performed by the double jet addition of the Ag+ salt solution and the Xxe2x88x92 salt solution for 1 second to 15 minutes, preferably for 10 seconds to 5 minutes, at pBr of from 1 to 3, preferably from 2 to 3, pH of from 1 to 12, preferably from 1.5 to 10, and temperature of from 0 to 50xc2x0 C., preferably from 0to 25xc2x0 C., and more preferably from 0 to 10xc2x0 C.
(80) The producing method of a silver halide emulsion as described in the above item (79), wherein the seed crystal is subjected to ripening after the nucleation to increase the ratio of the number of tabular grains by 1.5 to 105 times, preferably 5 to 105 times and then used as the seed crystal for growth.
(81) The producing method of a silver halide emulsion as described in the above item (79), wherein after the nucleation, the Ag+ salt solution and the Xxe2x88x92 salt solution are added to the crystal nuclei for 1 to 106 seconds, to thereby grow the projected area diameter of the tabular grain by 1.2 to 100 times, preferably from 2 to 100 times, and then the seed crystal emulsion is used for growth.
(82) The producing method of a silver halide emulsion as described in the above item (81), wherein the ratio of the number of tabular grains is increased by 2 to 104 times, and then the seed crystal is used for growth.
(83) The producing method of a silver halide emulsion as described in the above item (70), wherein the ratio of the mean diameter (d1) of the AgX0 to the mean thickness (d2) of the tabular seed grains (d1/d2) is 0.1 to 2.0, preferably 0.1 to 1.4, more preferably 0.3 to 1.2.
(84) The producing method of a silver halide emulsion as described in the above item (22), wherein the oxo acid species are HNO3 and/or H2SO4.
(85) The producing method of a silver halide emulsion as described in the above item (23), wherein the removing is carried out by the a1) method.
(86) The producing method of a silver halide emulsion as described in the above item (15), wherein the Met group content (xcexcmol/g) of the gelatin before the reducing process is preferably 3.1 to 70, more preferably 10 to 50.
(87) The producing method of a silver halide emulsion as described in the above item (15), wherein the Met group content (xcexcmol/g) of the gelatin after the reducing process is preferably 0to 30, more preferably 0 to 10.
(88) The producing method of a silver halide emulsion as described in the above item (2), wherein the solution containing Ag+ and the solution containing Xxe2x88x92 are introduced into the reaction vessel solution through tube hose directly under the surface, (the length of the tube hose under the surface/the diameter of the vessel) is preferably 0.5 to 50, more preferably 0.8 to 20, more preferably 1.5 to 20 in at least one tube hose, more preferably both tube hose.
(89) The producing method of a silver halide emulsion as described in the above item (2), (45) or (48), wherein the Ag+ addition rate (mol/minute) for producing AgX0, AgBr0, AgCl0 or AgI0 is preferably as follows: {the maximum addition rate during the precipitation/the addition rate of the first stage (0.1%, preferably 0.3% time duration of the total grain formation duration)}=1.6 to 1000, preferably 3 to 100.
(90) The producing method of a silver halide emulsion as described in the above item (2), (45) or (48), wherein the value of {the maximum addition rate during the precipitation/the addition rate of the last stage (0.1%, preferably 0.3% time duration of the total grain formation duration)} is 1.6 to 1000, preferably 3 to 100.
(91) The producing method of a silver halide emulsion as described in the above item (9) or (10), wherein the ratio [{100} crystal surface area/total surface area] of the AgBr0 seed grains produced during the nucleation stage is 10 to 100, preferably 20 to 100, more preferably 40 to 100, most preferably 70 to 100.
(92) The producing method of a silver halide emulsion as described in the above item (1), wherein the ratio [{100) crystal surface area/total surface area] of the AgBr0 grains is 10 to 100, preferably 20 to 100, more preferably 40 to 100, most preferably 70 to 100.
(93) The producing method of a silver halide emulsion as described in the above item (92), wherein the shape of the AgBr0 grain is a hexahedron, or a rounded one whose corners and/or edges are rounded, preferably a cubic grain or a rounded one, wherein the ratio {the curvature diameter (d3) of the round portion/the grain diameter (d4) } is 0.01 to 10, preferably 0.1 to 10.
(94) The producing method of a silver halide emulsion as described in the above item (1), (2), (3), (43) or (46), wherein at least one of the AgX0, AgBr0, AgCl0 and AgI0 is added to the silver halide emulsion containing seed grains after 10 to 106 sec (preferably 100 to 106, more preferably 103 to 106 sec) reservation after the formation of the AgX0, AgBr0, AgCl0 and AgI0.
(95) The producing method of a silver halide emulsion as described in the above item (94), wherein at least one of the AgX0, AgBr0, AgCl0 and AgI0 is added to the silver halide emulsion containing seed grains after the diameter of the AgX0, AgBr0, AgCl0 and AgI0 increases to 1.0 to 5 times,. preferably 1.01 to 5 times, more preferably 1.05 to 2 times, as large as just formed.
(96) The producing method of a silver halide emulsion as described in the above item (94), wherein at least one of the AgX0, AgBr0, AgCl0 and AgI0 is added to the silver halide emulsion containing seed grains after the variation coefficient of the diameter distribution of the AgX0, AgBr0, AgCl0 or AgI0 decrease to 10 to 99%, preferably 10 to 90% by the reservation.
(97) The producing method of a silver halide emulsion as described in the above item (94), wherein the reservation temperature is 0 to 70, preferably 2 to 50 xc2x0 C.
(98) The producing method of a silver halide emulsion as described in the above item (1), (2), (3) (43), (46) or (94), wherein at least one of the AgX0, AgBr0, AgCl0 and AgI0 is added to the silver halide emulsion containing seed grains after removing large grains whose diameter is larger than 2 times (preferably from 3 to 104 times) of average diameter by passing through a filter.
(99) The producing method of a silver halide emulsion as described in the above item (98), wherein the removing indicates that the value of the ratio [the removed large grains mole/the large grains mole before the removing] is 0.2 to 1.0, preferably 0.5 to 1.0, more preferably 0.7 to 1.0.
(100) The producing method of a silver halide emulsion as described in the above item (1), wherein the pH, pAg and pBr condition of the dispersing solution 2 for producing AgBr0 is existed in the region B1 in FIG. 5, preferably B2, more preferably B3, most preferably B4, wherein B1 region is surrounded by b1 line and pH 12.2, B2 region is surrounded by b1 line and pH 12.0.